University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-1967 Synthesis and Properties of Diorganomagnesium Compounds Conrad William Kamienski University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss., University of Tennessee, 1967. https://trace.tennessee.edu/utk_graddiss/3077 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: Bruce M. Anderson, George K. Schwitzer, David A. Shirley Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Novemb er 27, 1967 To the Graduate Council: I am submitting herewith a dissertation written by Conrad Wiliiam Kamienski entitled "Synthesis and Properties of Diorgano­ magnesium Compounds." I recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a maj or in Chemistry . We have read this dissertation and recommend its acceptance: Accepted for the Council: Vice President for Graduate Studies and Research SYNTHESIS AND PROPERTIES OF DIORGANOMAGNESIUM COMPOUNDS A Dissertation Presented to the Graduate Council of The University of Tennessee In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy by Conrad William Kamienski December 1967 To my dear wife , Diane 769836 ACKNOWLEDGEMENT The author wishes to acknowledge the kindness and generosity, as well as the guidance , shown him by Profeasor J. F. Eastham during his studies at the University of Tennessee and during the preparation of this thesis. Many thanks are also due to the Lithium Corporation of America and to the kindness , understanding and foresight of its president , Mr. Harry D. Feltenstein as well as the help of many other of its employees, without whose support this achievement could not have been possible. Gratitude is also due to the author' s father, Mr. Walter Warchalowski , and to other members of his family , for the wonderful guidance and understanding shown him throughout his career. A spec ial note of thanks mu st also be give� to Professor M. z. von Krzywoblocki of Michigan State University, wh ose kindness and advice inspired the author to pursue this course of study . iii TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION • • • • • • • • • • • • • • . • • • • • • • 1 A. Methods of Preparation of Dialkylmagnesium Compounds • • 1 B. Properties of Unsolvated Dialkylmagnesium Compounds 8 C. Solvation and the Properties of Dialkylmagnesium Compounds . 12 D. Relative Chemical Reactivity of Magnesium Alkyls and Grignard Reagents • • • • • • • • • • • • • • 18 E. Metallation and Polymerization by Magnesium Alkyls 2 6 II . RESULTS AND DISCUSSION • • • • • • • • • • • • 30 •• A. Preparation of Dialkylmagnesium Reagents . 30 1. Preparation of R2Mg by Metal-Metal Exchange between RLi and RMgCl or MgCl2 • • • • • 30 2. Direct Preparation of R2Mg from Magnesium Metal and Alkyl Chlorides • • • • • • • . 40 B. Physical Properties of Dialkylmagnesium Reagents 44 C. Complexes of Dialkylmagnesium Reagents with Bridgehead Diamines ••. •••••• 57 D. Me tallations with Dialkylmagnesium Reagents 60 E. Reactions of Dialkylmagnesium Reagents with Benzophenone • • • • • • • 78 F. Miscellaneous Reactions with Dialkylmagnesium Reagents • 85 iv ... .. v CHAP TER PAGE II . (CONTINUED) 1. Attemp ted Addition of Dialkylmagnesium Reagents to Ethylene • • • • • • • • . • • • • • 85 2. Attempted Reaction of di-,!.-Butylmagnesium Reagents with Phenyldimethylchlorosilane in Ethy l Ether, • • • • • • • • • • · • . .. 85 3. Effect of Dialkylmagnesium Reagents on the Halogen-Metal Interconversion Reaction with Alkyllithium Reagents . 86 G. Homologization 'of Alkyllithium Reagents • • • • • • • 81 1. Two Ordinary Runs . ' 88 2. Four TMEDA-Catalyzed Runs . 95 3. S-Butyllithium Run • . • i . 100 4. Summary . 103 : III . EXPERIMENTAL ••• . 107 A .. Introductory Information . • . • . • . 107 1. Reagents . • . • • • . • • 107 . 2. Instrumentation and Analytical Techniques • . '108 B. Preparation of Dialkyl�gnesium Reagents from Grignard and Organolithium Reagents . • • . 110 1. Preparation of Di-S-butylmagnesium . • • . • 110 2. Preparation of Methylisobutylmagnesium.• • • • 111 3. Preparation of Methyl-,!-butylmagnesium • . • . .. 112 4. Preparation of S-Butylphenylmagnesium .· • • • • • • 112 vi ·CHAPTER ·PAGE III. (CONTINUED) 5. Preparation of Diisobutylmagnesium • . 113 6. Preparation of Di-�-butylmagnesium from Simultaneous Preparation of.n-Butyllithium - and-�-Butylmagnesium Chloride . .. .114 C. Preparation of Dialkylmagnesium Reagents from Organolithium Reagents and Anhydrous Magnesium Chloride • • • • . 114 I 1. Preparation of Di-�-butylmagnesium . 114 a. From dimethyl ether-solvated by-product MgC12 . .. 114 b. From ether-desolvated �y-product MgC 12 . .. 115 c. From ether-desolvated MgC 12 by-product from reaction of a Grignard reagent with chlorine . • . 116 d. From dime thyl ether-solvated commercial anhydrous MgCl 2 . • 117 e. From ethyl ether-ac tivated, desolvated commercial anhydrous MgCl2 . • • • • . 118 f. From unsolvated by-product MgC12 •.••• , • 118 g. From unsolvated ball-milled lump commercial anhydrous MgC.l2 • • • • • • • • • • • • • . • 119 h. From alcohol-activated, desolvated commercial anhydrous MgC12 • • . • • • • •.• • • • • • • 120 i. From desolvated commercial MgCl2"6H20 • • • • 121 j. From commercial powdered anhydrous MgCl 2 • . 122 .. vii CHAPTER PAGE. III . · (CONTINUED) • • 2. Preparatien ef Eli-S-butylmagnesium • . • • • • • 122 a. From dimethy l ether-solvated by-product . •· . • • ' 122 b. From ether-desolvated MgC12 by�product from reac tion of a Grignard reagent with benzyl chloride . 123 3. Preparation of .Di-,!!-butylmagnesium. 124 ' 4. Preparation of .�ineopentyl magnesium • . .. 125 D. Direct Preparation of Dialkylmagnesium. Reagents From Magnesium Metal and Alkyl Chlorides • . 126· • • • 1. Preparation of ·:Di-,!-butylmagnesium • . 1.26 a. In dimethyl ether-cyclohexane solution • • 126 . b. By vacuum-stripping of solvent from the GrignaTd reagent , followed by re-solution . in benzene •• ••••. ••. 127 c. In diethyl ether-benzene solution . • . .. 127 • • 2. Preparation of Di-,!!�.lntylmagnesium • • • • • • 128 • • 3. Preparation of Di•,!!•8Dylmagnesium • • • • e-1 •.J .. 129 4. • Preparation of »iisopropylmagnesium . • • . • . e1 • •• 130 E. PrepaTation of Mixed Soluble Di-,n-�tylmaanes ium. Complexes with ,!·Butyllithium and. a-Butyl lithium 131 ' 1. Preparation of '»1-,!!·butyl•aneaium • • • • 131 2. Preparation of Butyllithium-Butylmaanesium Complexes . 132 viii CHAPTER P"AGE III. (CONTINUED) F. Preparation of Soluble , Mixed Dialkylmagnesium Complexes from Insoluble Dialkylmagnesium Compounds . •. 133 1. Preparation of a Soluble Diisobutyl -ni-L-butyl- magnesium Complex . 133 2 . Preparation of a Soluble Diisobutyl-Di- !-�tylmagnesium Complex • • • • • • • 133 3. Preparation of a Soluble D1-n•bu- tyl•Di -. ��butylmagnesium Complex • • • • • • • 133 · G. Insoluble Complexes of Dialkylmagnesium Reagents with Triethylenediamine and · Methyltriethyl�nediamine • • • . 134 1. Complexes with Triethylenediamine . 134 a. Di-L-butylmagnesium- triethylenediamine complex . 134 b. Other dialkylmagnesium- triethylenediamine complexes . 135 2 . Complexes with Methyltriethylenediamine . 136 a. Di -.!,.but¥lmag nesium-methyltriethylendiamine complex 136 . b. Other dialkylmagnesium-methyltriethylene- diamine complexes . 136 H. Metalations Effected with Dialkylmagnes ium Reagents 137 ix CHAPTER PAGE III. {CONTINUED) 1. Me tallation of Resorcinol Dimethyl Ether 137 a. In the ab sence of base . 137 b. In the presence of base 138 2. Me tallation of Thiophene ..• 139 a. Me tallation without Lewis base 139 b. Attempted metallation with Lewis base 140 c. Me tallation with THF plus potassium t-butoxide • • 140 d. Me tallation in the presence of �-butyl lithium plus TMEDA • 141 3 . Me tallation of n-Picoline 141 4. Metallation of Toluene • • 142 a. Attempted metallation 142 b. Me tallation with partially pyrolyzed di-�-butylmagnes ium 143 5. Metallat ion of Benzene with Partially Pyrolyzed Di-�-butylmagnesium 144 6. Me tallation of Alkynes • 145 a. Acetylene 145 b. 3 -Methyl-1-butyne 146 c. 4-Me thyl-1-pentyne • . 146 7. Me tallation of Dimethyl Sul foxide 147 I. Attempted Hy drogenolysis of Dialkylmagnesium Reagents • • • • • • . 148 X CHAPTER PAGE III. (CONT INUED) 1. With and Without Added TMEDA • • • • • • • • • 148 2 . In .the Presence of Potassium S-Butoxide Alone and witn Added THF and TMEDA • • • • • • • • 148 3. In the Presence